Perinone dyes



United States Patent ABSTRACT OF THE DISCLOSURE Acylamino-substituted perinone pigment dyes eminently suitable for the coloration of synthetic materials, in particular synthetic polyamides, in the melt.

This application is a continuation-in-part of application Ser. No. 528,361, filed Feb. 18, 1966, now abandoned.

Description The invention relates to perinone dyes of formula wherein P is a member selected from the group consisting of a mixture of monovalent radicals of formula the free valency bond coming from carbon atoms 3' and 4', a mixture of monovalent radicals of formula the free valency bond coming from carbon atoms 3' and 6, a monovalent radical of formula the free valency bond coming from carbon atom 6, and a mixture of bivalent radicals of formula the free valency bonds coming from carbon atoms 6 and 3', and 6 and 6, R is a member selected from the group consisting of cyclohexyl; naphthyl; unsubstituted phenyl; phenyl substituted by a member selected from the group consisting of fluorine, chlorine, alkyl having from 1 to 4 carbon atoms, trifluoromethyl and nitro; 4- (1,8-naphtha1ene-dicarboxylic acid imide)-phenyl; 4- (phenylcarbonylamino) phenyl; 4-[4'-(phenylcarbonylamino)-phenylcarbonylamino]-phenyl; 4 [4' (phenylsubstituted by a member selected from the group consist- 3,428,637 Patented Feb. 18, 1969 ing of fluorine, chlorine, alkyl having from 1 to 4 carbon atoms, trifiuoromethyl and nitro-carbonylamino)-phenylcarbonylaminoJ-phenyl; 4-(4'-phthaloylimino-phenyl-carbonylamino)-phenyl and 4-[4'-(1,8-nap-hthalene-dicarboxylic acid imide)-phenyl-carbonylamino]-phenyl and n is one of the numbers 1 or 2.

The process for the production of the dyes of Formula 1 consists of the condensation of n mols of a compound of formula HOOCR or of one of its functional derivatives, with 1 mol of an aminoperinone of formula.

P \NH2)n (III) Functional derivatives of an acid of Formula II are for example the anhydrides, esters of low molecular alcohols (having 1 to 4 carbon atoms) or the acid halides, in particular the acid chlorides.

Perinone dyes containing two or more aryl radicals in their A radicals can be produced in stages as follows: 1 mol of an aminoperinone is condensed with n mols of a carboxylic acid of formula HOOCArylZ (IV) where Z represents the nitro group, an acylamino group, a sulphonylamino group or the radical N=S=O, or with one of its functional derivatives as exemplified hereabove, the radical Z converted into the amino group, for example by reduction or saponification, the resulting compound again condensed with a carboxylic acid of Formula IV if desired, the substituent Z reduced or saponified to the amino group, and the compound finally condensed with n mols of a carboxylic acid of one of the formulae -OOOH COOH COOH or with one of their functional derivatives (as above exemplified).

The condensation reaction is carried out in water-free, inert solvents, for example chlorobenzenes, nitrobenzene or xylenes, at temperatures of 60 to 200 C. or preferably to C. It is usually of advantage to work in the presence of acid-binding agents, such as alkali carbonates or bicarbonates, alkali acetates, pyridine, dimethyl formamide or dimethyl aniline. The water formed in the reaction can be distilled off or driven out by a jet of gas conducted over the surface of the reaction mixture.

The reaction of the aminoperinones with a compound of Formula IV in which Z represents the nitro group can also be carried out in aqueous medium at a weakly acid to weakly alkaline reaction with the addition of an acid-binding agent.

The dyes conforming to the present invention are eminently suitable for the pigmentation of synthetic materials in the melt, in particular synthetic polyamides. These may be polycondensates or polymers of dicarboxylic acids and diamines, e.g. of adipic acid and hexamethylene diamine, of lactams, e.g. e-caprolactam, or of aminocarboxylic acid, e.g. w-aminoundecanoic acid. The dye is homogeneously mixed with the polyarnide melt which is then procesed by one of the normal methods, such as melt Spinning or injection, extrusion or transfer moulding.

French Patents 1,111,620 and 1,166,701 disclose similar perinone dyes, but the fastness properties of these, in particular the fastne-ss to light, washing and chlorine bleaching, are greatly inferior to those of the dyes of the present invention.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 A suspension of 28 parts of 6-amino-l, Z-naphthoylenebenzimidazole, 32 parts of 4-phthaloyliminobenzoyl chloride, 20 parts of anhydrous potassium carbonate and 1000 parts of chlorobenzene is heated for 16 hours at 120. The water thus formed is distilled off. 45 Parts of 6- 4"-phthaloylimino-benzoylamino) 1, Z-naphthoylenebenzimidazole are obtained. This is suspended in 1000 parts of pyridine and 20 parts of hydrazine hydrate and the solution boiled for 2 hours. After dilution with water 20 parts of 6-(4-aminobenzoylamino)-1, Z-naphthoylcue-benzimidazole are obtained. This product can also be obtained by reacting 6-amino-1, 2-naphthoylenebenzimidazole with 4-nitrobenzoy1 chloride with subsequent reduction of the nitro group.

A suspension of 2.0 parts of 6-(4"-aminobenzoylamino)-1, Z-naphthoylene-benzimidazole, 30 parts of 4-benzoylaminobenzoyl chloride, 10 parts of anhydrous potassium carbonate and 500 parts of chlorobenzene is heated at 120 for 16 hours, the water formed being distilled off. 37 Parts of the yellow compound 6-(4"- benzoylamino 4"- benzoylamino-benzoylamino) 1, 2- naphthoylene-benzimidazole of the formula are obtained.

Dyeing Example 5 parts of a dye obtained according to Example 1 are mixed with 1000 parts of poly-s-caprolactam, which is then melted at 285 under nitrogen and spun. A dyed filament is obtained which is very fast to light, rubbing, sublimation and wet treatments and is suitable for the normal textile manufacturing processes.

EXAMPLE 2 A suspension of 10.8 parts of 6-amino-1, Z-naphthoylene-benzimidazole, 150 parts of chlorobenzene and 5 parts of dimethylaniline is heated at 88 parts of benzoyl chloride are dropped in and the stated temperature maintained for a further 2 hours or so until the starting product is no longer indicated. After isolation and purification 16 parts of a dye of formula are obtained.

EXAMPLE 3 50 parts of a mixture of 6,3'- and 6,6-dinitro-1,'2-naphthoylene-benzirnimidazole, as obtained by nitration in accordance with Coll. Czech. Chem. Commun, 28, 3352 (1963), are reduced with hydrogen in 1000 parts of dimethyl formamide in the presence of 5 parts of Raney nickel. 40 parts of a mixture of the corresponding diamino compounds are obtained. 6 parts of this mixture are suspended in 100 parts of chlorobenzene and brought to the boil, on which 10 parts of benzoyl chloride are added and boiling continued until no further starting product is indicated. After isolation and purification approximately 8 parts of the corresponding dibenzoylaminoperinones are obtained.

Dyes similar to those of Examples 2 and 3 are obtained when 6-amino-1,Z-naphthoylene-benzimidazole or a mixture of 6,3'- and 6,6-diamino-1,Z-naphthoylene-benzimidazole is reacted in an analogous manner with other cyclic carboxylic acid chlorides in equimolar ratio. Examples of such carboxylic acid chlorides are 4-methylbenzoic acid chloride, 4-trifluormethyl-benzoic acid chloride, 4-tertitary-butyl benzoic acid chloride, 4-nitrobenzoic acid chloride, 4-chlorobenzoic acid chloride, 4-fiuorobenzoic acid chloride, 2,4- and 3,4-dichlorobenzoic acid chloride, ocand fl-naphthalenecarboxylic acid chloride and cyclohexane-carboxylic acid chloride.

EXAMPLE 4 A suspension of 5.7 parts of 6-amino-1,2-naphthoylenebenzimidazole and 7.3 parts of peri-naphthoyleneiminobenzoic acid chloride in parts of anhydrous water-free dichlorobenzene is stirred at until no further starting material is indicated. On isolation and purification about 10 parts of a yellow dye are obtained which has the formula substituted by an amino group in the 3- or 4'-position EXAMPLE 5 are dissolved in 1000 parts of water-free dichlorobenzene A suspension of parts of p and heated at 150-160" with stirring, upon which 32 parts thoylene'beflzimidazole, 150 Parts of chlol'obenlelle and of benzoyl chloride are added and stirring continued 5 Rafts f dimethylanill'fle i's'heated at 10 Parts of at the same temperature until no further starting product y chloriqe are added dropwise d Stirring is indicated. After isolation and purification 60-65 parts colltlnued at 111ml I further Starting Product is indi' of a heterogeneous dye are obtained having the formula cated. The nitro compound is isolated and reduced in the known way, e.-g. by catalytic action with Raney nickel H or NaHS, to the amino compound.

Condensation of 6-amino 1,2 naphthoylene-benzi- 1O midazole and 4-nitrobenzoyl chloride can also be carried N out in aqueous medium. 71.5 parts of 6 amino 1,2- naphthoylene-benzimidazole in finely divided form are C suspended in 2 litres of water, an excess of 4-nitrobenzoyl chloride is added, followed by sodium carbonate and, if necessary, pyridine or dirnethyl formamide, on which the EXAMPLE 8 suspension is vigorously stirred at room temperature until on analogous lines to Example 7, 40 parts of F starting Product is no longsr indivated' Work benzoyl chloride, in place of 32 parts of benzoyl chloride, mg 95-100 Parts of 20 are reacted with the mixture of aminoperinones, after naphthoylene-benzirnidazole are obtained; this can be rewhich the nitro group is reduced to the amino group in to '(4l"ammol.jenzoylammo)'12'naphthylene as the known way, e.g. with Raney nickel. 80 parts of the descnbedm the foregoing resulting amine are suspended in 1000 parts of water-free 8 parts of the r?sI1 1nng 'ammobenzoylammo)'l'z dichlorobenzene with the addition of 63 parts of 4- naphthoylenebelfzlmldazfle and 641mm 5 benzoylaminobenzoyl chloride and stirred at ISO-160 minobenzoic acld chlonde are dlssolved m 130 Parts until the starting product is no longer indicated. 0n of Water-free dichlorobenzene and stirred at 150 until working up approximately arts of a heterogeneous no further starting product is indicated. After isolation dye ar bt i d whi h h s th formula and purification about 12 parts of a yellow dye is obtained which has the formula EXAMPLE 6 8 Parts of aminobellzoylefmino) 1,2 In place of the benzoyl chloride used in Example 7 thoylene'beifzlmldazok P Example and 7 or of the 4-benzoylaminobenzoyl chloride used in Exparts of peri-naphthoyleneimlnobenzolc acid chlorlde are ample 8 equimolar amounts of the Cyclic earboxylie dissolved in 200 parts of water-free chlorobenzene and acid chlorides enumerated in the final paragraph of 5 parts of pyridine and the solution is bolied with reample 3ean be used flux until no further amine is indicated. The product is 13 parts of a yellow dye of formula N NH-C OONH-C 00-N\ EXAMPLE 7 EXAMPLE 9 57 parts of a mixture of the perinone of formula 62 parts of a mixture of perinones of formula amino-substituted in 3'- or 6'-position, are suspended in 1000 parts of water-free dichlorobenzene and heated at ISO-160 with stirring. After the addition of parts of 4-nitrobenzoy1 chloride stirring is continued at the same temperature until the starting product is no longer indicated, on which the final product, (4-nitrobenzoyl)-aminoperinone, is isolated and purified. After reduction of the nitro group parts of the resulting amine are heated in 1000 parts of Water-free dichlorobenzene at ISO-160, then 30 parts of 4-benzoylaminobenzoyl chloride are added and stirring continued until no starting product is indicated. On working up about parts of a dark red dye are obtained.

Examples of representative dyes of the foregoing examples are as follows:

EXAMPLE 1 the free valency bond coming from carbon atoms 3 and 6', a monovalent radical of formula the free valency bonds coming from carbon atoms 6 and 3, and 6 and 6,

o as- NHGO NHCO NHCO EXAMPLE 2 ii 071v NHOOQ Q -C=N- EXAMPLE 4 EXAMPLE 5 Having thus disclosed the invention, what we claim is: 1. Pcrinone pigmented dyes of formula wherein P is a member selected from the group consisting of a mixture of monovalent radicals of formula the free valency bond coming from carbon atoms 3' and 4', a mixture of monovalent radicals of formula R is a member selected from the group consisting of cyclohexyl; naphthyl; unsubstituted phenyl; phenyl substituted by a member selected from the group consisting of fluorine, chlorine, alkyl having from 1 to 4 carbon atoms, trifluoromethyl and nitro; 4-(1,8- naphthalene-dicarboxylic acid imide) -phenyl; 4- (phenyl carbonylamino) phenyl; 4-[4'-(phenylcarbonylamino) phenylcarbonylamino]-phenyl; 4-[4- phenyl-substituted by a member selected from the group consisting of fluorine, chlorine, alkyl having from 1 to 4 carbon atoms, trifluoromethyl and nitrocarbonylamino) -phenyl carbonylamino1-phenyl; 4- (4'-phthaloylimino phenyl carbonylamino)phenyl and 4 [4 (1,8 naphthalene dicarboxylic acid imide)-pheny1-carbonylarnino]-phenyl and n is one of the number-s 1 or 2.

2. The dye according to claim 1 of formula 9 10 3. The dye according to claim 1 of formula 4. The dye according to claim 1 of formula 4 co 0 o a N NHCO 45 a NHCO N 5 .434 O=N-- CO 5. The dye according to claim 1 of formula References Cited FOREIGN PATENTS 1,489,369 7/1967 France.

ALEX MAZEL, Primary Examiner. D. G. DAVIS, Assistant Examiner.

U.S. Cl. X.R. 260282, 326, 515, 281; 855

P0405) UNITED STATES PA'TEIJT OFFICE Inv '1iavcr Pijstmand Ku1-l Ulr-ich Steiner It is certified that error appears in the abovo identifigd patent and that said Letters Patent are hereby corrected as shown below:

[ 4 Column 3, line 12;, correct "processed"; line 60, "1," should mad -l,---. Column 1;, line 25, "28, 3352" should read ----28, 3352,----; line 13, correct "tertiam Column 5, line 1 5, in the formula, "-NO should read -NH- line 60, in the fornmla, "0'' should read --C-- in the structure line 70, in the fomtula, "3" should read ---3'-- and "I should read --l;'--. Colwm 6, line 32, in the fomnlla, "C H should read -C H Column 7, line 5 "pigmented" should read --pig,mm1t-; line 70, in tfie formula, the missing bond should be inserted between positions 3' and 2' as Colunm 10, line 10, in the formula of claim 5, "NHCH" should read --.IHCO-.

SIGGED AND SEALED MAR 3 1970 R Am Edward M. Fletcher, Ir.

WILLIAM E- W, J LAttesung Comissioner of Patent 

